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EP0403993B1 - Procédé pour la préparation de L-ascorbate de sodium ou de potassium - Google Patents

Procédé pour la préparation de L-ascorbate de sodium ou de potassium Download PDF

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Publication number
EP0403993B1
EP0403993B1 EP90111414A EP90111414A EP0403993B1 EP 0403993 B1 EP0403993 B1 EP 0403993B1 EP 90111414 A EP90111414 A EP 90111414A EP 90111414 A EP90111414 A EP 90111414A EP 0403993 B1 EP0403993 B1 EP 0403993B1
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EP
European Patent Office
Prior art keywords
keto
gulonic acid
sodium
process according
methyl ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90111414A
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German (de)
English (en)
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EP0403993A1 (fr
Inventor
Tomislav Keglevic
Christoph Klein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Enco Engineering Chur AG
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Enco Engineering Chur AG
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Publication of EP0403993A1 publication Critical patent/EP0403993A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/62—Three oxygen atoms, e.g. ascorbic acid

Definitions

  • the present invention relates to a process for the production of sodium or potassium L-ascorbate using 2-keto-L-gulonic acid, in which 2-keto-L-gulonic acid methyl ester is formed and is lactonized by adding bicarbonate.
  • the esterification equilibrium limits the yield.
  • a long cooking time is usually chosen in order to achieve a high degree of esterification and thus a satisfactory yield.
  • Both the 2-L-keto-gulonic acid and its methyl ester are not very stable thermally. They can disintegrate at the required reaction temperatures.
  • the decay products and the unreacted 2-keto-L-gulonic acid represent impurities in the end product, the removal of which requires considerable effort.
  • the Reichstein process is therefore unsuitable or at least not economical for the production of sodium L-ascorbate as end product in a purity sufficient for pharmaceutical purposes.
  • the esterification of the 2-keto-L-gulonic acid with methanol in particular is therefore only carried out partially, ie not until the esterification equilibrium is reached.
  • the process according to the invention therefore only requires very short reaction times in the esterification, owing to the utilization of the range of high reaction rates and the switching off of the range of low reaction rates. This is advantageously associated with a significantly lower incidence of decomposition products.
  • the process according to the invention is distinguished by a high purity of the ester solution. Unreacted 2-keto-L-gulonic acid and impurities such as the aforementioned decomposition products and also the soluble proteins mentioned at the outset, which originate from the fermentative production of the 2-keto-L-gulonic acid monohydrate, are precipitated and separated off in the intermediate step mentioned.
  • the method according to the invention enables the direct production of pharmaceutically pure sodium or potassium L-ascorbate in the course of the L-ascorbic acid synthesis.
  • a mixture of 2-keto-gulonic acid monohydrate and sodium 2-keto-gulonate can be used to obtain the 2-keto-L-gulonic acid methyl ester, the proportion of the sodium salt being up to 50%.
  • the mixture of 50% monodydrate and 50% salt is more stable than the pure monohydrate.
  • the salt In the case of a high salt content, the salt must first be converted into the acid, which is done by adding a sufficient amount of concentrated sulfuric acid.
  • the sulfate formed is preferably separated off separately before the addition of bicarbonate. This separation can advantageously also take place before the addition of the amount of concentrated sulfuric acid catalyzing the esterification. If the proportion of the sodium salt in the mixture used is not too high and is only a few%, it is also possible to dispense with the separate removal of the sulfate. It is then removed together with the precipitation caused by the addition of bicarbonate.
  • a temperature in the range between 60-75 ° C. is preferably set for the esterification.
  • the esterification in the presence of concentrated sulfuric acid in a catalytic amount to accelerate the reaction is preferably carried out within 15 to 90 minutes, depending on the degree of contamination of the starting product.
  • the amount of bicarbonate required to precipitate the precipitate must be sufficient not only to neutralize the 2-keto-L-gulonic acid still present but also to neutralize the sulfuric acid used.
  • the bicarbonate is preferably added to the esterification solution in a slight excess (over the amount required per se for neutralization) of 1-2%. During and after the addition of the bicarbonate, the mixture is stirred for half an hour to two hours, preferably at a constant temperature of about 60 ° C.
  • the precipitation is preferably separated off by filtration, but in principle all solid / liquid separation methods can be used.
  • the sodium or potassium bicarbonate required for lactonization can be added directly to the ester solution obtained after the precipitate has been separated off.
  • the following route can also be used to produce high-purity ascorbate:
  • the after the separation of the The precipitated ester solution is cooled (to about 0 ° C.) and, in the process, precipitated esters (partially) precipitated out, preferably again by filtration.
  • the ester obtained in pure form is dissolved in methanol and the process is continued with this ester solution.
  • the process can also be continued with the mother liquor from which the methyl ester has (partly) precipitated due to cooling, since this still contains enough methyl ester.
  • the ascorbate obtained in this way is impure, but is still useful for certain applications.
  • the solution it contains is preferably boiled at 60-67 ° C. for only 30 to 180 minutes after the addition of the further sodium or potassium bicarbonate.
  • the sodium or potassium L-ascorbate obtained in suspension is preferably separated off again by filtration.
  • the separated ascorbate can advantageously also be washed with methanol.
  • the yield that can be achieved can be increased in an advantageous manner in that the precipitate separated off in the aforementioned intermediate step is used as the starting material instead of fresh 2-keto-L-gulonic acid monohydrate is reused.
  • the separated precipitate which depending on the degree of esterification still contains 3 - 10% of the unesterified starting product, is dissolved with methanol instead of fresh 2-keto-L-gulonic acid monohydrate, preferably in a separate solution, in the same way as described above, subjected to esterification, precipitation and separation of the precipitate.
  • the precipitation that occurs again is discarded. It only contains insignificant amounts of the starting product, but the unwanted impurities in a relatively high concentration.
  • the remaining liquid which contains the 2-keto-L-gulonic acid methyl ester, is subsequently either added to the similar liquid remaining from the original batch after the precipitation has been separated off and thus reintroduced into the original process, or further separately, but in an analogous manner Way, worked up to ascorbate.
  • the filter residue (l0.7 g) (filter residue A) is treated in a parallel solution with 24 ccm methanol with the addition of 1.3 ccm H2SO4 at 67-68 ° C for 30 minutes (esterification B). Subsequently, 1.3 g of sodium bicarbonate are metered in and stirred for one hour at 50 ° C. (cases B). The precipitate formed (6.7 g) is filtered off (Filtration B / I), the filter residue (filter residue B) is discarded. The filtrate (filtrate B) is then lactonized for three hours with bicarbonate (lactonization B) and the ascorbate formed (product B) is finally isolated again by filtration (filtration B / II).
  • esterification A The same esterification batch as in example 1 is kept at 67-68 ° C. for one hour (esterification A) and then stirred with l2.5 g of sodium bicarbonate for two hours at 60 ° C. (cases A).
  • filter residue A The aforementioned filter residue (filter residue A) is in turn esterified as in Example 1 in 24 ccm of methanol with 1.3 ccm of H2SO4 for one hour (esterification B) and the solution is subsequently mixed with 1.3 g of sodium bicarbonate at 60 ° C. for half an hour Hour treated (cases B). The precipitate is filtered off and the filter residue (filter residue B) is discarded.
  • a batch of 100 g of 2-keto-L-gulonic acid monohydrate, 325 cc of methanol and 5.5 cc of H 2 SO 4 is added to 10 g of filter residue, for example the type of Example 1 (filter residue A).
  • the solution is then esterified for one hour at 67-68 ° C. (esterification A) and subsequently treated with 13.5 g of sodium bicarbonate under the same conditions as in the previous examples.
  • Example 1 100 g of 2-keto-L-gulonic acid monohydrate is treated as in Example 1 (esterification A, cases A, filtration A / I).
  • the resulting filter residue (filter residue A) is subsequently further treated as in Example 1 (esterification B, cases B, filtration B / I).
  • the result is a second filtrate (filtrate B) and again a filter residue (filter residue B).
  • the latter is discarded.
  • the two filtrates (filtrate A and filtrate B) are mixed and boiled with bicarbonate for two hours.
  • a mixture (50 g) of 2-keto-L-gulonic acid (5 l, 57%) and sodium 2-keto-L-gulonate (48.43%) is suspended in methanol (130 ml) and 4.5 ml of concentrated sulfuric acid admitted.
  • the suspension is refluxed for one hour with stirring and then filtered to remove the sodium sulfate formed (4.77 g).
  • Sodium bicarbonate (7.0 g) is added to the filtrate and the suspension is heated under reflux for a further hour with stirring.
  • 2-Keto-L-gulonic acid monohydrate (300 g, l, 415 mol) is placed in a 1000 ml glass reaction vessel and methanol is added (780 ml). Sulfuric acid (3 ml) is added dropwise with stirring and the reaction solution is refluxed for one hour (68 ° C). The solution mentioned is then cooled to 60 ° C., 3 l, 2 g of sodium bicarbonate are added, and the stirring and heating at reflux are continued for a further hour. The precipitate contained in the reaction solution is separated off by filtration. It will contain 33.19 g of dry sediment, which contains 48% of the 2-keto-L-gulonic acid as the sodium salt. The filtrate is cooled to 5 ° C.
  • the ascorbate obtained is still recrystallized. To do this, it is dissolved in 20 ml of distilled water. The solution is filtered and then 40 ml of methanol are added. The resulting suspension is cooled down to 0 ° C. and the desired product is filtered off and dried. 14.44 g of pharmaceutically pure sodium ascorbate is obtained with a purity of 99.34%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Furan Compounds (AREA)
  • Saccharide Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Claims (12)

  1. Procédé pour la préparation du L-ascorbate de sodium ou de potassium au moyen de l'acide 2-céto-L-gulonique, dans lequel du 2-céto-L-gulonate de méthyle est formé et lactonisé par addition de bicarbonate, caractérisé par les étapes de processus suivantes:
       obtention du 2-céto-L-gulonique de méthyle par dissolution d'un mélange contenant de l'acide 2-céto-L-gulonique monohydraté, dans du méthanol, en présence d'acide sulfurique concentré, en quantité au moins catalytique;
       addition, selon le produit final recherché, de bicarbonate de sodium ou de bicarbonate de potassium en une quantité suffisante pour la précipitation, dans la solution, de l'acide 2-céto-L-gulonique monohydraté non estérifié ainsi que d'impuretés présente, mais non suffisante pour la lactonisation du 2-céto-L-gulonate de méthyle avant que soit atteint l'équilibre de la réaction d'estérification;
       séparation du précipité;
       addition, selon le produit final recherché, de bicarbonate de sodium ou de bicarbonate de potassium, pour la lactonisation du 2-céto-L-gulonate de méthyle; et
       séparation du L-ascorbate de sodium ou du L-ascorbate de potassium résultant de la lactonisation, qui se trouve en suspension.
  2. Procédé selon la revendication 1, caractérisé en ce que ledit mélange, contenant de l'acide 2-céto-L-gulonique monohydraté, contient en outre du 2-céto-L-gulonate de sodium et en ce que la quantité totale d'acide sulfurique concentré mesurée est telle qu'elle suffit essentiellement également à la conversion du 2-céto-L-gulonate de sodium en acide 2-céto-L-gulonique.
  3. Procédé selon la revendication 2, caractérisé en ce que, lors de la conversion du 2-céto-L-gulonate de sodium en acide 2-céto-L-gulonique, le sulfate de sodium formé est séparé par filtration avant l'addition de bicarbonate.
  4. Procédé selon la revendication 3, caractérisé en ce que l'on n'utilise d'abord pratiquement que la quantité d'acide sulfurique concentré qui est requise pour la conversion du 2-céto-L-gulonate de sodium en acide 2-céto-L-gulonique, et en ce que l'on n'ajoute la quantité d'acide sulfurique concentré qui catalyse l'estérification qu'après la séparation par filtration du sulfate de sodium formé.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que l'estérification de l'acide 2-céto-gulonique par le méthanol s'effectue en seulement 15 à 90 minutes, selon le degré de la contamination du produit de départ, à 60-70°C, jusqu'à un degré d'estérification de 87 à 91 %.
  6. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que, après la première addition de bicarbonate de sodium ou de bicarbonate de potassium, on agite pendant 30-120 minutes le mélange à une température constante, de préférence d'environ 60° C, pour la séparation du précipité.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on refroidit jusqu'à une température dans la plage comprise entre 0 et 5°C le liquide restant après la séparation du précipité et on sépare le 2-céto-L-gulonate de méthyle ainsi précipité.
  8. Procédé selon la revendication 7, caractérisé en ce que le bicarbonate de sodium ou bicarbonate de potassium requis pour la lactonisation du 2-céto-L-gulonate de méthyle est ajouté au liquide qui reste après la séparation du précipité et la séparation du 2-céto-L-gulonate de méthyle précipité sous l'effet de l'abaissement de température.
  9. Procédé selon la revendication 7, caractérisé en ce que l'on dissout à nouveau dans du méthanol le 2-céto-L-gulonate de méthyle séparé et en ce que l'on ajoute à cette solution le bicarbonate de sodium ou bicarbonate de potassium requis pour la lactonisation du 2-céto-L-gulonate de méthyle.
  10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que le liquide contenant du 2-céto-L-gulonate de méthyle, auquel est ajouté la nouvelle quantité de bicarbonate de sodium ou de potassium aux fins de lactonisation de cet ester, est chauffé pendant 30 à 180 minutes à 60-67°C, après cette addition.
  11. Procédé selon l'une des revendications 1 à 10, caractérisé en ce que l'on introduit à nouveau dans le processus le précipité séparé, en tant que produit de départ, au lieu d'acide 2-céto-L-gulonique monohydraté neuf.
  12. Procédé selon la revendication 10, caractérisé en ce que l'on réutilise le précipité séparé, au lieu d'acide 2-céto-L-gulonique monohydraté neuf, dans un mélange de départ en solution séparé, et en ce que l'on rejette le précipité formé dans ce mélange de départ en solution.
EP90111414A 1989-06-20 1990-06-18 Procédé pour la préparation de L-ascorbate de sodium ou de potassium Expired - Lifetime EP0403993B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2377/89 1989-06-20
CH2377/89A CH678057A5 (de) 1989-06-26 1989-06-26 Verfahren zur herstellung von natrium- oder kalium-l-ascorbat.

Publications (2)

Publication Number Publication Date
EP0403993A1 EP0403993A1 (fr) 1990-12-27
EP0403993B1 true EP0403993B1 (fr) 1992-09-23

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EP90111414A Expired - Lifetime EP0403993B1 (fr) 1989-06-20 1990-06-18 Procédé pour la préparation de L-ascorbate de sodium ou de potassium

Country Status (9)

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US (1) US5128487A (fr)
EP (1) EP0403993B1 (fr)
JP (1) JP2868158B2 (fr)
CN (1) CN1031569C (fr)
AT (1) ATE80880T1 (fr)
CA (1) CA2019741A1 (fr)
CH (1) CH678057A5 (fr)
DE (1) DE59000315D1 (fr)
DK (1) DK0403993T3 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1036457C (zh) * 1991-10-01 1997-11-19 武田药品工业株式会社 2-酮基-l-古洛糖酸低级烷基脂的制备方法
EP0671405A1 (fr) * 1994-01-18 1995-09-13 F. Hoffmann-La Roche Ag Procédé de préparation d'esters de l'acide céto-2 L gulonique
CN1050356C (zh) * 1995-11-24 2000-03-15 中原制药厂 L-抗坏血酸钠或钾的制备方法
JP3976832B2 (ja) * 1996-04-30 2007-09-19 ディーエスエム アイピー アセッツ ビー．ブイ． ２−ケト−ｌ−グロン酸の単離方法
DE19938980A1 (de) 1999-08-19 2001-02-22 Basf Ag Verfahren zur Herstellung von 2-Keto-L-gulonsäureestern
US6670505B1 (en) 2000-03-07 2003-12-30 Eastman Chemical Company Process for the recovery of organic acids from aqueous solutions
US6320061B1 (en) 2000-06-05 2001-11-20 Eastman Chemical Company Solvent exchange process
ATE295843T1 (de) 2000-12-22 2005-06-15 Eastman Chem Co Kontinuierliches verfahren zur herstellung von l- ascorbinsäure
WO2002051827A1 (fr) * 2000-12-22 2002-07-04 Eastman Chemical Company Procede de preparation d'un acide ascorbique en presence d'un sulfite
US6740762B2 (en) 2001-08-24 2004-05-25 Eastman Chemical Company Process for ascorbic acids using alkaline earth silicate catalysts
US6716997B1 (en) 2001-10-09 2004-04-06 Eastman Chemical Company Systems and methods for generation of ascorbic acid with reduced color
CN1711276A (zh) 2002-11-11 2005-12-21 巴斯福股份公司 制备2－酮基－l－古洛糖酸c4－c10－烷基酯的方法
CN101139290B (zh) * 2007-09-14 2010-05-26 浙江工商大学 酯化反应-渗透汽化膜分离集成工艺生产维生素c的方法
CN101451206B (zh) * 2007-11-30 2010-12-29 中国科学院金属研究所 一种超高强度钛合金
CN103102335A (zh) * 2012-11-15 2013-05-15 江苏江山制药有限公司 粗维生素c母液回收生产粗维生素c钠的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2179978A (en) * 1936-06-06 1939-11-14 Hoffmann La Roche Process for the manufacture of levo-ascorbic acid
US2462251A (en) * 1945-05-16 1949-02-22 Merck & Co Inc Process for preparing ascorbic acids
GB1029393A (en) * 1962-06-22 1966-05-11 Merck & Co Inc 2-keto-d-gluconic acid concentration
US4180511A (en) * 1978-09-22 1979-12-25 Pfizer Inc. Ascorbic acid process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Helv. Chim. Acta 17, 311, 1934. *

Also Published As

Publication number Publication date
DK0403993T3 (da) 1992-10-26
US5128487A (en) 1992-07-07
EP0403993A1 (fr) 1990-12-27
JP2868158B2 (ja) 1999-03-10
CA2019741A1 (fr) 1990-12-26
CN1031569C (zh) 1996-04-17
DE59000315D1 (de) 1992-10-29
ATE80880T1 (de) 1992-10-15
JPH0338579A (ja) 1991-02-19
CH678057A5 (de) 1991-07-31
CN1048387A (zh) 1991-01-09

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